CN104609541A - Sebacic acid wastewater direct biochemical treatment method without desalination - Google Patents
Sebacic acid wastewater direct biochemical treatment method without desalination Download PDFInfo
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Abstract
The invention relates to a sebacic acid wastewater direct biochemical treatment method without desalination. The method comprises the following steps: storing sebacic acid wastewater at normal temperature in an open space in order to age the wastewater; directly cultivating salt-tolerant anaerobic florae and salt-tolerant hydrolysis acidification florae in the aged wastewater with the sodium sulfate content of 5-15% to finally obtain salt-tolerant anaerobic active sludge and salt-tolerant hydrolysis acidification active sludge; and inoculating the sludge, directly treating the sebacic acid wastewater through a hydrolysis acidification + aerobic treatment technology to make the F/M value in a hydrolysis acidification pool and an aerobic pool be 0.1-0.4 and 0.2-1.0 respectively, and carrying out biochemical treatment under conditions on inlet water with the sodium sulfate content of 5-15%, the COD of below 5000mg/L and the volatile phenol content of below 200mg/L to make biochemical outlet water with the COD of below 100mg/L and the volatile phenol content of 0.5mg/L. The method disclosed in the invention solves a problem that sebacic acid wastewater cannot be directly treated through traditional biochemical methods, and the wastewater treatment cost of the method is greatly lower than that of an evaporation technology and other technologies.
Description
Technical field
The present invention relates to a kind for the treatment of process containing high sodium sulfate trade effluent, specifically a kind of sebacic acid factory effluent that makes is in the method for not diluting direct biochemical treatment under not desalination condition.
Background technology
Sebacic acid a kind ofly important has valency industrial chemicals, is widely used in production engineering plastics, fire-resistant lubricants, epoxy curing agent, sebacic anhydride, ucon oil, alcohol phenol resins, vibrin, Glass Fiber Reinforcement, makeup etc.China is the country that sebacic acid output is maximum in the world, mainly adopting with Viscotrol C is at present the cracking process production technique of raw material, product per ton need consume 150 ~ 250kg phenol, produce 25 ~ 40 tons of waste water, wherein phenol content is 2000 ~ 5000mg/L, pH is 2 ~ 3, sodium sulphate content is 6 ~ 10%, COD content is 10000 ~ 20000mg/L.Sebacic acid waste water belongs to high salt, high phenol, high-COD waste water; According to estimates, the sebacic acid enterprise of a 40000t/a produces waste water 1,500,000 tons/a, if this waste water does not carry out improving process, can cause severe contamination to environment.
The current industrial main method of extraction or absorption that adopts processes sebacic acid waste water, can remove most of phenols in waste water, even make phenol up to standard, but still be not enough to make waste water quality completely up to standard.Such as: utilize ricinolic acid to extract sebacic acid waste water, extraction progression more than 8 grades, though need not back extraction be carried out, water average COD > 4000mg/L, phenol > 50mg/L after extraction; Utilize sec-octyl alcohol as extraction agent, water COD > 2000mg/L after extraction, phenol concentration is greater than 50mg/L; Utilize QH-1 type complexometric extraction that Phenol for Waste Water content can be made to be down to below 10mg/L, but raffinate COD > 1000mg/L.Therefore, sebacic acid wastewater treatment be made up to standard, must process further the waste water after extraction, main method comprises advanced oxidation and biochemical treatment, comparatively speaking, if energy biochemical treatment, will have cost advantage.
But sodium sulphate content is up to 5 ~ 15% in sebacic acid waste water, to common micro-organisms cell, there is murder by poisoning and restraining effect, and in anaerobic biochemical treatment process, also easily there is sulfate reduction generation H in contains sodium sulfate waste water
2s, therefore conventional activated sludge process can not be used for the direct biochemical treatment of sebacic acid waste water.Therefore, in prior art, sebacic acid factory effluent is through except after phenol pre-treatment, first carries out evaporative desalination, then carries out qualified discharge after biochemical treatment to evaporation condensed water, or reuse after advanced treatment further.If directly biochemical treatment can be carried out and qualified discharge without evaporative desalination, greatly will reduce sebacic acid waste water treatment cost, improve the situation that current sebacic acid production industry Pollution abatement cost is high.
Summary of the invention
The object of the invention is the deficiency for existing sebacic acid wastewater processing technology, propose a kind of method that can make the direct biochemical treatment of sebacic acid waste water not desalination, use the method can make COD < 100mg/L after sebacic acid wastewater treatment.
Principle of the present invention is:
Contains sodium sulfate 5 ~ 15% in sebacic acid waste water, mainly containing organic pollutants is phenol, lipid acid and small molecular organic acid, and wastewater biochemical is good generally.But in the fresh wastewater that sebacic acid production plant is discharged, phenol concentration reaches 2000 ~ 5000mg/L, and water temperature, more than 50 DEG C, is wherein difficult to there is microbial survival.But through removing the pretreated sebacic acid waste water of phenol, wherein phenol concentration is generally down to 50 ~ 150mg/L, and bio-toxicity reduces greatly.If this waste water places the long period at normal temperatures, the contact of long period is carried out with external environment, microbes in surrounding soil, dust, empty G&W contacts with each other, and the microorganism in these environment is introduced in sebacic acid waste water, wherein part microorganism can adapt to sebacic acid waste water quality environment gradually in the long-term ageing process of waste water, and and finally can grow using the organism in waste water as carbon source and the energy.In addition on the one hand, the high sodium sulfate wastewater that sebacic acid production process produces, can interact with the environment such as the soil of on-site, air and rainwater under open working condition, therefore, have in the sebacic acid enterprise surrounding environment of certain production time to exist and obtain the adaptive salt-durable microbe of sebacic acid waste water quality by natural selection effect.
Technical problem to be solved by this invention is realized by following technical scheme.The present invention is the direct biochemical processing method of a kind of sebacic acid waste water not desalination, be characterized in: the method is COD < 100mg/L after making sebacic acid wastewater treatment when waste water does not dilute not desalination by biochemical method, and its key step comprises:
(1) cultivation of salt tolerant aerobic activated sludge: directly cultivate the aerobic flora of salt tolerant with sebacic acid ageing waste water; Initial sebacic acid ageing influent waste water COD < 500mg/L, total salt are 5 ~ 15%; HRT > 12h, dissolved oxygen DO > 0.5mg/L in culturing process; As the clearance > 80% of COD or phenol, improve influent COD, continue cultivation 2 ~ 10d; Have after nutrient solution opacity increases and leaves standstill and can occur by sedimentation flco, continue to improve influent COD, maintain F/M < 1.0 and continue cultivation 5 ~ 30d, obtaining salt tolerant aerobic activated sludge sebacic acid waste water under aerobic conditions to aerobic degradation ability;
The sebacic acid waste water of at least 1 month is stored open under described sebacic acid ageing waste water refers to normal temperature;
(2) cultivation of salt tolerant hydrolysis souring activity mud: inoculation salt tolerant aerobic activated sludge, to hydrolysis acidification pool, directly cultivates salt tolerant acidication flora with sebacic acid waste water; Initial influent COD < 500mg/L, total salt are 5 ~ 15%, HRT > 12h, dissolved oxygen DO < 0.5mg/L in culturing process; As COD clearance > 20%, improve influent COD, maintain F/M=0.1 ~ 0.4 and continue cultivation 30 ~ 90d, obtain the salt tolerant hydrolysis souring activity mud under anoxic conditions sebacic acid waste water to acidication function;
(3) biochemical treatment of sebacic acid waste water: the mud that step (2) and step (1) obtain is inoculated into hydrolysis acidification pool and Aerobic Pond respectively, adopts " acidication+aerobic " technique to process sebacic acid waste water; Acidication segment process parameter is: influent COD < 5000mg/L, HRT are 8 ~ 48h, MLSS is 4000 ~ 20000mg/L, F/M=0.1 ~ 0.4; Aerobic section processing parameter is: HRT is 12 ~ 48h, MLSS is 2000 ~ 5000mg/L, dissolved oxygen 2.0 ~ 4.0mg/L, F/M=0.2 ~ 1.0.
In the direct biochemical processing method of a kind of sebacic acid waste water of the present invention not desalination, preferred technical scheme or technical characteristic are further:
1. first adopt extraction or macroporous resin method to carry out except phenol pre-treatment sebacic acid factory effluent, processed waste water COD < 5000mg/L, volatile phenol < 200mg/L, then carry out ageing and obtain sebacic acid ageing waste water.
2., in step (1), (2) and (3), supplement N, P, K on demand as nutritive element.
3. with 5 ~ 15% aqueous sodium persulfate solution dilution sebacic acid ageing waste water or sebacic acid waste water to reduce initial stage influent COD.
4. salt tolerant aerobic activated sludge inoculum size >=500mg/L in step (2).
5. in step (3), salt tolerant aerobic activated sludge and salt tolerant hydrolysis souring activity sludge seeding amount are respectively 1000 ~ 20000mg/L, 500 ~ 5000mg/L.
6. step (1) sebacic acid ageing influent waste water pH is 5.0 ~ 6.0.
Below technical solution of the present invention is further elaborated:
1. sebacic acid waste water of the present invention, refers to and carries out except the pretreated waste water of phenol, wherein volatile phenol < 200mg/L, COD < 5000mg/L to sebacic acid factory effluent; The art methods such as ricinolic acid extraction, sec-octyl alcohol extraction, complexometric extraction, macroporous resin adsorption are comprised except phenol method.
2. sebacic acid ageing waste water of the present invention refers to the waste water after deposit for some time at normal temperatures except the pretreated sebacic acid waste water of phenol.Waste water in ageing process by the salt-durable microbe in natural selection effect screening and enrichment surrounding environment.Therefore, waste water digestion time should be longer as far as possible, increases the time of natural selection effect, thus improve ageing process to the selective enrichment effect of salt-durable microbe; Ageing can also be carried out in the environmental sample such as soil, water sample to waste water by adding near sebacic acid production plant.
3. in step (2), salt tolerant aerobic activated sludge both can as the bacterium source of cultivating acidication flora, and also simultaneously as the dirt settling of acidication flora, thus initial inoculum should be higher, is preferably not less than 500mg/L.
4. in step (3) Aerobic Pond, salt tolerant aerobic activated sludge initial inoculum is preferably 500 ~ 5000mg/L, and in hydrolysis acidification pool, salt tolerant hydrolysis souring activity sludge seeding amount is preferably 1000 ~ 20000mg/L.Because aerobic sludge rate of propagation is very fast, initial inoculation concentration can be low a little; But acidication sludge growth speed is relatively slow, and initial inoculation concentration is preferably higher.
5. if desired sebacic acid waste water is diluted, reduce the influent COD of the invention process starting stage, should dilute with 5 ~ 15% aqueous sodium persulfate solutions.
6. contain more lipid acid in sebacic acid waste water, in Hydrolysis Acidification, pH can raise, different from general acidication feature; Therefore, inlet flow-patterm can maintain slightly acidic, and namely pH is 5.0 ~ 6.0, thus reduces soda acid consumption.
7. in sebacic acid waste water, nitrogen phosphorus etc. is relative with the nutritive element that salt-durable microbe grows lacks, N, P, the K that therefore at least should supplement the nutrients in element.
Compared with prior art, the invention has the beneficial effects as follows:
(1) sebacic acid waste water directly COD < 200mg/L, volatile phenol < 0.5mg/L after biochemical treatment, solving conventional biochemical method can not directly to the difficult problem that sebacic acid waste water processes.
(2) utilizing sebacic acid waste water self to cultivate the aerobic salt-durable microbe flora of directly turning out adaptation sebacic acid waste water quality under hypersaline environment of salt tolerant, without the need to being separated or pure culture halophilic bacterium, reducing enforcement difficulty.
(3) adopt biochemical method directly to process the high-salt wastewater of contains sodium sulfate 5 ~ 15%, significantly reduce cost for wastewater treatment relative to techniques such as evaporations.
Embodiment
Below in conjunction with specific embodiment, content of the present invention is described, so that those skilled in the art understand further to the present invention.
Embodiment 1, the direct biochemical processing method of a kind of sebacic acid waste water not desalination, the method is COD < 100mg/L after making sebacic acid wastewater treatment when waste water does not dilute not desalination by biochemical method, and its key step comprises:
(1) cultivation of salt tolerant aerobic activated sludge: directly cultivate the aerobic flora of salt tolerant with sebacic acid ageing waste water; Initial sebacic acid ageing influent waste water COD < 500mg/L, total salt are 5%; HRT > 12h, dissolved oxygen DO > 0.5mg/L in culturing process; As the clearance > 80% of COD or phenol, improve influent COD, continue cultivation 2 ~ 10d; Have after nutrient solution opacity increases and leaves standstill and can occur by sedimentation flco, continue to improve influent COD, maintain F/M < 1.0 and continue cultivation 5 ~ 30d, obtaining salt tolerant aerobic activated sludge sebacic acid waste water under aerobic conditions to aerobic degradation ability;
The sebacic acid waste water of at least 1 month is stored open under described sebacic acid ageing waste water refers to normal temperature;
(2) cultivation of salt tolerant hydrolysis souring activity mud: inoculation salt tolerant aerobic activated sludge, to hydrolysis acidification pool, directly cultivates salt tolerant acidication flora with sebacic acid waste water; Initial influent COD < 500mg/L, total salt are 5%, HRT > 12h, dissolved oxygen DO < 0.5mg/L in culturing process; As COD clearance > 20%, improve influent COD, maintain F/M=0.1 and continue cultivation 30 ~ 90d, obtain the salt tolerant hydrolysis souring activity mud under anoxic conditions sebacic acid waste water to acidication function;
(3) biochemical treatment of sebacic acid waste water: the mud that step (2) and step (1) obtain is inoculated into hydrolysis acidification pool and Aerobic Pond respectively, adopts " acidication+aerobic " technique to process sebacic acid waste water; Acidication segment process parameter is: influent COD < 5000mg/L, HRT are 8 ~ 48h, MLSS is 4000mg/L, F/M=0.1; Aerobic section processing parameter is: HRT is 12 ~ 48h, MLSS is 2000mg/L, dissolved oxygen 2.0mg/L, F/M=0.2.
Embodiment 2, the direct biochemical processing method of a kind of sebacic acid waste water not desalination, the method is COD < 100mg/L after making sebacic acid wastewater treatment when waste water does not dilute not desalination by biochemical method, and its key step comprises:
(1) cultivation of salt tolerant aerobic activated sludge: directly cultivate the aerobic flora of salt tolerant with sebacic acid ageing waste water; Initial sebacic acid ageing influent waste water COD < 500mg/L, total salt are 15%; HRT > 12h, dissolved oxygen DO > 0.5mg/L in culturing process; As the clearance > 80% of COD or phenol, improve influent COD, continue cultivation 2 ~ 10d; Have after nutrient solution opacity increases and leaves standstill and can occur by sedimentation flco, continue to improve influent COD, maintain F/M < 1.0 and continue cultivation 5 ~ 30d, obtaining salt tolerant aerobic activated sludge sebacic acid waste water under aerobic conditions to aerobic degradation ability;
The sebacic acid waste water of at least 1 month is stored open under described sebacic acid ageing waste water refers to normal temperature;
(2) cultivation of salt tolerant hydrolysis souring activity mud: inoculation salt tolerant aerobic activated sludge, to hydrolysis acidification pool, directly cultivates salt tolerant acidication flora with sebacic acid waste water; Initial influent COD < 500mg/L, total salt are 15%, HRT > 12h, dissolved oxygen DO < 0.5mg/L in culturing process; As COD clearance > 20%, improve influent COD, maintain F/M=0.4 and continue cultivation 30 ~ 90d, obtain the salt tolerant hydrolysis souring activity mud under anoxic conditions sebacic acid waste water to acidication function;
(3) biochemical treatment of sebacic acid waste water: the mud that step (2) and step (1) obtain is inoculated into hydrolysis acidification pool and Aerobic Pond respectively, adopts " acidication+aerobic " technique to process sebacic acid waste water; Acidication segment process parameter is: influent COD < 5000mg/L, HRT are 8 ~ 48h, MLSS is 20000mg/L, F/M=0.4; Aerobic section processing parameter is: HRT is 12 ~ 48h, MLSS is 5000mg/L, dissolved oxygen 4.0mg/L, F/M=1.0.
Embodiment 3, the direct biochemical processing method of a kind of sebacic acid waste water not desalination, the method is COD < 100mg/L after making sebacic acid wastewater treatment when waste water does not dilute not desalination by biochemical method, and its key step comprises:
(1) cultivation of salt tolerant aerobic activated sludge: directly cultivate the aerobic flora of salt tolerant with sebacic acid ageing waste water; Initial sebacic acid ageing influent waste water COD < 500mg/L, total salt are 10%; HRT > 12h, dissolved oxygen DO > 0.5mg/L in culturing process; As the clearance > 80% of COD or phenol, improve influent COD, continue cultivation 2 ~ 10d; Have after nutrient solution opacity increases and leaves standstill and can occur by sedimentation flco, continue to improve influent COD, maintain F/M < 1.0 and continue cultivation 5 ~ 30d, obtaining salt tolerant aerobic activated sludge sebacic acid waste water under aerobic conditions to aerobic degradation ability;
The sebacic acid waste water of at least 1 month is stored open under described sebacic acid ageing waste water refers to normal temperature;
(2) cultivation of salt tolerant hydrolysis souring activity mud: inoculation salt tolerant aerobic activated sludge, to hydrolysis acidification pool, directly cultivates salt tolerant acidication flora with sebacic acid waste water; Initial influent COD < 500mg/L, total salt are 10%, HRT > 12h, dissolved oxygen DO < 0.5mg/L in culturing process; As COD clearance > 20%, improve influent COD, maintain F/M=0.2 and continue cultivation 30 ~ 90d, obtain the salt tolerant hydrolysis souring activity mud under anoxic conditions sebacic acid waste water to acidication function;
(3) biochemical treatment of sebacic acid waste water: the mud that step (2) and step (1) obtain is inoculated into hydrolysis acidification pool and Aerobic Pond respectively, adopts " acidication+aerobic " technique to process sebacic acid waste water; Acidication segment process parameter is: influent COD < 5000mg/L, HRT are 8 ~ 48h, MLSS is 10000mg/L, F/M=0.2; Aerobic section processing parameter is: HRT is 12 ~ 48h, MLSS is 3500mg/L, dissolved oxygen 3.0mg/L, F/M=0.6.
Embodiment 4, in the method for embodiment 1-3 described in any one: first adopt extraction or macroporous resin method to carry out except phenol pre-treatment to sebacic acid factory effluent, processed waste water COD < 5000mg/L, volatile phenol < 200mg/L, then carry out ageing and obtain sebacic acid ageing waste water.
Embodiment 5, in the method for embodiment 1-4 described in any one: in step (1), (2) and (3), supplements N, P, K on demand as nutritive element.
Embodiment 6, in the method for embodiment 1-5 described in any one: the aqueous sodium persulfate solution dilution sebacic acid ageing waste water with 5 ~ 15% or sebacic acid waste water are to reduce initial stage influent COD.
Embodiment 7, in the method for embodiment 1-6 described in any one: salt tolerant aerobic activated sludge inoculum size >=500mg/L in step (2).
Embodiment 8, in the method for embodiment 1-7 described in any one: in step (3), salt tolerant aerobic activated sludge and salt tolerant hydrolysis souring activity sludge seeding amount are respectively 1000 ~ 20000mg/L, 500 ~ 5000mg/L.
Embodiment 9, in the method for embodiment 1-8 described in any one: step (1) sebacic acid ageing influent waste water pH is 5.0 ~ 6.0.
Embodiment 10, the direct biochemical processing method experiment of a kind of sebacic acid waste water not desalination:
Certain enterprise's sebacic acid factory effluent, COD is 12000 ~ 15000mg/L, and phenol content is 3000 ~ 4000mg/L, and sodium sulphate content is 6 ~ 10%, adopts ricinolic acid to carry out multi-stage solvent extraction except phenol to waste water, reclaims the phenol in waste water simultaneously.After removing phenol pre-treatment, waste water COD is 3500 ~ 4200mg/L, and phenol content is 50 ~ 150mg/L, pH is 5.0 ~ 6.0.
Get above-mentioned except in phenol pretreated sebacic acid waste water 200L loading plastic tank, be placed in plant area, at room temperature carry out ageing 4 months.After waste water ageing terminates, with 5 ~ 15% aqueous sodium persulfate solutions by part ageing wastewater dilution to COD < 500mg/L, volatile phenol < 50mg/L.Get 500mL waste water, supplement urea and potassium primary phosphate, shaking culture 48h.Leave standstill or centrifugal rear discharge supernatant liquor, supplement waste water and the follow-up persistent oscillation cultivation of N, P.3 ~ 10 cycles of cultivation like this, each cycle 20 ~ 30h, can be observed solution opacity increase and have can sedimentation flco occur; By sedimentation, filtration or centrifugal after flco to transfer in 6L device aeration and cultivate, progressively improve influent COD, maintain F/M=0.4 ~ 1.0 and also continue cultivation 5 ~ 10d, activated sludge concentration constantly increases, and is salt tolerant aerobic activated sludge.
The salt tolerant aerobic activated sludge inoculating above-mentioned cultivation cultivates salt tolerant hydrolysis souring activity mud to 2L hydrolytic tank, and initial sludge seeding amount is 500 ~ 1000mg/L, does not first enter waste water, and mud is dallied 2 ~ 5d under anoxic condition.After mud blackout, enter sebacic acid waste water, initial influent COD < 500mg/L, total salt 5 ~ 15%, retention time of sewage 20 ~ 30h, dissolved oxygen DO < 0.5mg/L; As COD clearance > 20%, show that salt tolerant acidication flora is formed.Increase influent COD, maintain F/M=0.1 ~ 0.4 and continue cultivation 30 ~ 60d, can cultivate and obtain salt tolerant hydrolysis souring activity mud.
Adopt " acidication+aerobic " art breading sebacic acid waste water, inoculate above-mentioned mud respectively to 2L hydrolysis acidification pool and 4L Aerobic Pond.Hydrolysis acidification pool is Anaerobic Contact pond, and Aerobic Pond is MBBR pond.Hydrolysis acidification pool sludge seeding amount is about 5000mg/L, and Aerobic Pond sludge seeding amount is about 3000mg/L; Hydrolysis acidification pool HRT=24h, Aerobic Pond HRT=48h; Hydrolysis acidification pool F/M=0.1 ~ 0.4; Aerobic Pond F/M=0.4 ~ 0.6; Hydrolysis acidification pool dissolved oxygen DO < 0.5mg/L, Aerobic Pond dissolved oxygen 2.0 ~ 4.0mg/L; It is 6.0 ~ 9.0 that pH controls, and water temperature is 25 ~ 35 DEG C; Successfully start after 15 ~ 30d, finally can make COD < 100mg/L, volatile phenol < 0.5mg/L after sebacic acid wastewater treatment.
Embodiment 11, the direct biochemical processing method experiment of a kind of sebacic acid waste water not desalination:
Certain enterprise's sebacic acid factory effluent, COD is 12000 ~ 18000mg/L, and phenol content is 2000 ~ 4000mg/L, and sodium sulphate content is 6 ~ 12%, adopts sec-octyl alcohol to carry out extraction except phenol to waste water, reclaims the phenol in waste water simultaneously.After removing phenol pre-treatment, waste water COD is 2500 ~ 3000mg/L, and phenol content is 50 ~ 100mg/L.
Getting above-mentioned except carrying out ageing, digestion time 2 months, temperature average out to 30 ~ 35 DEG C between aging period under phenol pretreated sebacic acid waste water 50L room temperature, not doing other process.With 5 ~ 15% aqueous sodium persulfate solutions by wastewater dilution to COD < 500mg/L, volatile phenol < 50mg/L, supplement urea, potassium primary phosphate, get 500mL shaking culture.Detect the palliating degradation degree of COD and phenol in culturing process, as the degradation rate > 80% of COD or phenol, centrifugal rear discharge supernatant liquor, adds sebacic acid ageing waste water and N, P nutrition, continues shaking culture.So repeat cultivation 3 ~ 5 times, solution opacity, after leaving standstill, have flco to occur and sedimentation.Transfer in 6L aerating apparatus, aeration is cultivated, and progressively improves influent COD, controls dissolved oxygen DO > 0.5mg/L, sludge loading F/M=0.2 ~ 0.5; Cultivation 15 ~ 30d like this, sludge concentration is increased to 1000 ~ 2000mg/L, and continue water inlet and cultivate, sludge concentration can further improve.
Inoculate above-mentioned salt tolerant aerobic activated sludge and cultivate salt tolerant hydrolysis souring activity mud to the hydrolytic tank of 6L, not aeration, provides anaerobic environment in the mode of intermittent stirring, and acidication active sludge is selected in domestication gradually.Initial sludge seeding amount is 1000 ~ 1500mg/L, and first do not enter waste water, trace element supplement, continuously stirring runs 2 days, and mud turns black gradually.Start into sebacic acid waste water, discharge 2 ~ 3L supernatant liquor, initial influent COD < 500mg/L, churning time is 12 ~ 24h about; Each cycle is analyzed and measures COD clearance and VFA changing conditions after stirring and terminating, and as COD clearance > 20% and VFA increases by more than 20%, shows that salt tolerant acidication flora is formed.Increase influent COD with 20 ~ 50% ratios, maintain F/M=0.1 ~ 0.4 and cultivate 40 ~ 60d, activated sludge concentration increases, and successfully cultivates and obtains salt tolerant hydrolysis souring activity mud.
The salt tolerant hydrolysis souring activity mud that inoculation above-mentioned steps is cultivated and the actual sebacic acid waste water of salt tolerant aerobic activated sludge process.Hydrolysis acidification pool is UASB form, sludge seeding amount 20000mg/L; Aerobic Pond is divided into two sections, " MBBR+MBR ", sludge seeding amount 2000mg/L; The hydrolysis acidification pool residence time 15 ~ 20h, the Aerobic Pond residence time 36 ~ 48h; Hydrolysis acidification pool F/M=0.1 ~ 0.4; Aerobic Pond F/M=0.4 ~ 0.6; Hydrolysis acidification pool dissolved oxygen DO < 0.5mg/L, Aerobic Pond dissolved oxygen 2.0 ~ 4.0mg/L; It is 6.0 ~ 9.0 that pH controls, and water temperature is 25 ~ 35 DEG C; Start successfully through 15 ~ 30d, finally can make COD < 100mg/L, volatile phenol < 0.5mg/L after sebacic acid wastewater treatment.
Embodiment 12, the direct biochemical processing method experiment of a kind of sebacic acid waste water not desalination:
Certain enterprise's sebacic acid factory effluent, COD is 12000 ~ 15000mg/L, and phenol content is 3000 ~ 4000mg/L, adopts HLE type complexing extractant to carry out extraction and back-extraction to waste water and gets, reclaim the phenol in waste water simultaneously.After removing phenol pre-treatment, waste water COD is 1000 ~ 1200mg/L, and phenol content is 10 ~ 40mg/L.
Getting that above-mentioned between aging period, temperature is 30 ~ 35 DEG C except carrying out ageing, digestion time 6 months under phenol pretreated sebacic acid waste water 50L room temperature, not doing other process.With 5 ~ 15% aqueous sodium persulfate solutions by wastewater dilution to COD < 500mg/L, volatile phenol < 50mg/L, supplement urea, potassium primary phosphate, get 6000mL aeration cultivate 24 ~ 48h.Leave standstill half an hour, discharge 1/2 supernatant liquor, add the sebacic acid ageing waste water after after dilution and N, P nutrition, continue aeration and cultivate, controlling dissolved oxygen DO is 0.5 ~ 4.0mg/L.3 ~ 5 cycles of cultivation like this, solution opacity increase and leave standstill after have can sedimentation flco occur.Progressively improve influent COD, controlling dissolved oxygen DO is 2.0 ~ 4.0mg/L, F/M=0.4 ~ 0.6; Cultivation 10 ~ 20d like this, sludge concentration is increased to more than 1000mg/L, and continue water inlet and cultivate, sludge concentration can further improve.
Inoculate above-mentioned salt tolerant aerobic activated sludge and cultivate salt tolerant hydrolysis souring activity mud to the hydrolytic tank of 6L, not aeration, provides anaerobic environment in the mode of intermittent stirring, and acidication active sludge is selected in domestication gradually.Initial sludge seeding amount is about 2000mg/L, does not first enter waste water, and continuously stirring runs 2 ~ 4 days, and mud turns black gradually.Start into sebacic acid waste water, each cycle discharges 3L supernatant liquor, enters 3L waste water, stirs 8 ~ 24h, quiescent settling 0.5 ~ 2h, analyzes and measures COD clearance.Initial influent COD < 500mg/L, when COD clearance > 20% also keeps stable, shows that salt tolerant acidication flora begins to take shape.Increase influent COD with 20 ~ 50% ratios, maintain F/M=0.1 ~ 0.4 and continue cultivation 60 ~ 90d, salt tolerant hydrolysis souring activity culturing sludge is to more than 4000mg/L.
The salt tolerant hydrolysis souring activity mud that inoculation above-mentioned steps is cultivated and the actual sebacic acid waste water of salt tolerant aerobic activated sludge process.Hydrolysis acidification pool sludge seeding amount 5000 ~ 10000mg/L, Aerobic Pond sludge seeding amount 2000 ~ 4000mg/L; The hydrolysis acidification pool residence time 20 ~ 30h, the Aerobic Pond residence time 36 ~ 48h; Hydrolysis acidification pool F/M(sludge loading)=0.1 ~ 0.4; Aerobic Pond F/M=0.4 ~ 0.6; Hydrolysis acidification pool dissolved oxygen DO < 0.5mg/L, Aerobic Pond dissolved oxygen 2.0 ~ 4.0mg/L; It is 6.0 ~ 9.0 that pH controls, and water temperature is 25 ~ 35 DEG C; Start successfully through 15 ~ 30d, finally can make COD < 100mg/L, volatile phenol < 0.5mg/L after sebacic acid wastewater treatment.
Claims (7)
1. the direct biochemical processing method of sebacic acid waste water not desalination, is characterized in that: the method is COD < 100mg/L after making sebacic acid wastewater treatment when waste water does not dilute not desalination by biochemical method, and its key step comprises:
(1) cultivation of salt tolerant aerobic activated sludge: directly cultivate the aerobic flora of salt tolerant with sebacic acid ageing waste water; Initial sebacic acid ageing influent waste water COD < 500mg/L, total salt are 5 ~ 15%; HRT > 12h, dissolved oxygen DO > 0.5mg/L in culturing process; As the clearance > 80% of COD or phenol, improve influent COD, continue cultivation 2 ~ 10d; Have after nutrient solution opacity increases and leaves standstill and can occur by sedimentation flco, continue to improve influent COD, maintain F/M < 1.0 and continue cultivation 5 ~ 30d, obtaining salt tolerant aerobic activated sludge sebacic acid waste water under aerobic conditions to aerobic degradation ability;
The sebacic acid waste water of at least 1 month is stored open under described sebacic acid ageing waste water refers to normal temperature;
(2) cultivation of salt tolerant hydrolysis souring activity mud: inoculation salt tolerant aerobic activated sludge, to hydrolysis acidification pool, directly cultivates salt tolerant acidication flora with sebacic acid waste water; Initial influent COD < 500mg/L, total salt are 5 ~ 15%, HRT > 12h, dissolved oxygen DO < 0.5mg/L in culturing process; As COD clearance > 20%, improve influent COD, maintain F/M=0.1 ~ 0.4 and continue cultivation 30 ~ 90d, obtain the salt tolerant hydrolysis souring activity mud under anoxic conditions sebacic acid waste water to acidication function;
(3) biochemical treatment of sebacic acid waste water: the mud that step (2) and step (1) obtain is inoculated into hydrolysis acidification pool and Aerobic Pond respectively, adopts " acidication+aerobic " technique to process sebacic acid waste water; Acidication segment process parameter is: influent COD < 5000mg/L, HRT are 8 ~ 48h, MLSS is 4000 ~ 20000mg/L, F/M=0.1 ~ 0.4; Aerobic section processing parameter is: HRT is 12 ~ 48h, MLSS is 2000 ~ 5000mg/L, dissolved oxygen 2.0 ~ 4.0mg/L, F/M=0.2 ~ 1.0.
2. method according to claim 1, it is characterized in that: first adopt extraction or macroporous resin method to carry out except phenol pre-treatment to sebacic acid factory effluent, processed waste water COD < 5000mg/L, volatile phenol < 200mg/L, then carry out ageing and obtain sebacic acid ageing waste water.
3. method according to claim 1, is characterized in that: in step (1), (2) and (3), supplements N, P, K on demand as nutritive element.
4. method according to claim 1, is characterized in that: the aqueous sodium persulfate solution dilution sebacic acid ageing waste water with 5 ~ 15% or sebacic acid waste water are to reduce initial stage influent COD.
5. method according to claim 1, is characterized in that: salt tolerant aerobic activated sludge inoculum size >=500mg/L in step (2).
6. method according to claim 1, is characterized in that: in step (3), salt tolerant aerobic activated sludge and salt tolerant hydrolysis souring activity sludge seeding amount are respectively 1000 ~ 20000mg/L, 500 ~ 5000mg/L.
7. method according to claim 1, is characterized in that: step (1) sebacic acid ageing influent waste water pH is 5.0 ~ 6.0.
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